Alkyl carbamates in color compositions



Patented June 3, 1947 V ALKYL CARBAMATES m COLOR COMPOSITIONS Roy Herman Kienle and Chester Albert Amick, Bound Brook,-N. J., assignors to American CyanamidCompany, New York, N. Y., a corporation of Maine No Drawing. Application July 1, 1943', i Serial No. 493,129

- This invention relates to a new type of dyeing and printing assistant, dye compositions containing these assistants andproducts printed therefrom. i i i Use of printing-color pastes containing dyes, particularly in printing operations using vat dyes, is'sufiiciently well-known so that the procedure has become almost standardized. The actual color source may be either a dye paste or a dye powder. In addition to the real color, a dye paste usually 12 Claims. (01. 8-70) contains, agents to prevent drying-out, settling and/or freezing. Dye powders, not being subject to these difficulties, do not require these agents ut they usually contain agents or areso processed aslto promote dispersibility.

In either case, the dye paste or dye powder must be admixed with suitable thickener, usually a sum dispersion, to form a printing-color paste which is suitable for application. In the case of vat dyes, it is also necessary to adda reducing agent and usually an alkali. Because the color yield from printing-color pastes often decreases rapidly as the paste ages after being made up, these printingcolorpastes are usually prepared by the fabric finishers just before they are to be used.

The printing-color pastes, however compounded,,are then applied to textile, paper; or other fabric materials for decorative or protective purposes.; The printed pieces are dried, aged in a steam ager, treated with an oxidizing agent, rinsed and finally dried, Usually in processing textiles, the printedfabric also is soaped at or near the boil withabout a- 0.1% soap solution and again rinsed before the finaldrying operation.

In making up and applying printing-color pastes it has been found that a material suitable for use as a printing assistant is of advantage in obtaining maximum color yield. The exact way in which these materials act to producean improved color yield in printing is not entirely un-,; derstood. It is with these printing-aids or assistants that the present invention is particularly concerned. 1

Although printing aids are desirable in the printing-color pastes, the exactpoint at which they are added may vary. 'Dye pastes may con-.

tain printing aids as oneoftheircomponents and printing-color pastes ma'dejtherefrom will obvious'ly contain the printing assistant. Where a printing assistant is not present inthe dye paste, it may be added at the time of making up the printing-color paste. v v

It is preferable, however, that the printing assistant be incorporated in the actual dye paste. Their addition at'the properlpoint in the manu- 2 t facture of the paste-isnot only easier, but in addition they are thus generally more uniformly dispersed throughout a printing-color paste ma'de therefrom. Asa result, the printing assistants usually operate more effectively when the printing-color pasteis finallyapplied to the fabric. a f

It is only relatively recently that dye powders suitable for use in making up I printing-color pastes have been available. Most of the printing aids previously used in dye pastes, being either liquid in form or extremely hydroscopic, can not be used with dye powders, the latter being -necessarily limited to the use of dry solids. Nevertheless, it is desirable thatprinting assistants be incorporated in the powders at the time of nianuf which apply in the facture for the same reasons case of dye pastes.

Dye pastes containing various liquid printing assistants have been made. Among the liquid materials used are the a kylol amines, for example,

triethanol amine; and/or polyhydric alcohols such as glycerine, glycol, diethylene glycol andthe like. Various derivatives therefrom also have,

been tried. If a printing aid is to be incorporated in a dye powder, a solidprinting aid is necessary.

Examples of such solids which have been used in v the past include the hydrochlorides of alkylol amines; silver salt (sodium anthraquinone betasulfonate) anthraquinone and certain metal salts 1 such as those of cobalt and iron. i

Unfortunately, most of these printing aids pre viously used are not as satisfactory asmay be desired. Many of them will not in all cases produce the intensification of color forwhich. they were intended. Others, such as the polyhydricalcohols,

cause deterioration of the printing-color pastes so that marked variations in the'strength of prints,

therefrom are observable even after the printingcolor paste has been allowed .to standfor, only a l w relatively short time. Many of them are satisfactorywith some colors but have an adverse effeet onothers, even to the extent of visibly alter ing the shade. None of them are suitable without modification for use both in paste and powder compositions.

There remains, therefore, a demand for suitable printing assistants which will produce a satisfactory color intensification and will not cause deterioration of the dyeing or printing composition on standing. Preferably also, the. assistants should beruseful both with dye pastes and dye powders and in addition should be readily available orcheaply andeasily prepared; It is, therew fore, the object of the present invention to pro.

3 vide anew type of printing assistant which possesses these desirable properties.

In general, the object of the present invention is accomplished by'making use of a solid urethane... Accorldir'rgtcthe presentginv'entiom the expression a methane?" is intended 'to in'clude not only urethane itself, but also those solid alkyl carbarnates which are the reaction products" f,

of a monohyclric aliphatic alcohol and. a. urea or substituted urea, particularly the alkyl-sub'st tuted ureas. So far as the present invention is concerned the urethanes may be added to: the

printing-color pastes at any-point in theirzicom pounding. They may be in'corporated into the thickener; into the dye pastes or powders or may be blended into the printing-color.paste when the latter composition is prepared. However; as;

pointed out above, it is preferable that they be 4 way of limitation. All parts are by weight unless otherwise noted.

Example 1 A paste;was"preparedgby gslurrying 2,900 parts of. :11? iBritish. gum (Stein. 'I-l'all) in- 5.,000 parts of water and the mixture was heated with con- 'tinuous stirring until the temperature reached about 185? F. Heating was continued for about hours after which 450 parts of powdered potassium carbonate and 450 parts of powdered sodiumflcarbonategwere added and the mixture incorporated in the dye paste or powderduringtheir manufacture.

I Theiusesofthis new-class of printi-ng assistants POSsesses: anumber of, important. advantages. Most 05 these products: are dry powders but aresoluble or. dispersible-in dye-paste suspensions: so that they may-- be'used inall cases: They do not cause.- deterioration of-the: printing-color pastes on: standing They encourage the production of excellent; color yields ,evenunder hot ageingcondit-ions Their use is simple ince they maybe employed as powders, as suspensionsint: water or as.alcoholic;solutions, producing excellent color yields.- whatever the mode/of admixture.

pro'ducinggthe alkyl. carbamates of the present invention: it is not necessary to limit'the assistant to. the: reaction product of any particular monohyd-ric alcohol. Substantially anyrnonohydric aliphatic alcohol of from: about threetotwelve carbon atoms can be reacted w ithan urea or; amassed-urea to produc'e a. carbamateusefur: according" to. the pres nt inv nti n; While t intended to. be. so

th mvehtfitn is it" .that th'luse'offl V atic aleoiims having v four t,oei'ght artcn atcms' ppeartegive when'y sanmar -prec ncts;

ethyl'jdi'eth b'iityl ethyl nitrosbi eta pla en 111'832.

off'theipresentfinventionare not limited to the needy any p' rticu ar" dye forms, they are sp" 'c'iallyfsuit'abl'e or us'elwith vat'g yes' in "e'oi'pbwd'er" term. Particularly good j aybe 'ob taiinedfus'ih'g 'the vat-avepow. dfer tr high aut'o'di'sper'sib'ility set forth in era 1- y t ar, Reissue Baten't Np. 21,402; re arch 19; 194-0. fay combining the "color osition? containingthe" assistants ofthe present irivenfti'on,, the fun advantages of both. may be gaine'dwitli' afre'su'ltan't excellence of shade and sharpnessof color: j

Printing pastesrnad'e in this way have the, par ticular advantage that the dyes remain'in' a highly dispersed state as individual'p'artic'les rather than asdispeifsions of particle aggregates. In the pres erit specification and claiin s, wh'erfe. hig h1y-dis-' persed" dyes are referred to, reference to p ast'es inWhiCh-thed'ye particlesare so disperse'd'is inl connection with the followingexaniples' which" areihtend'ed t'obe illustrative ot llyand not by .e ll en't results have been obtained; for exam le; usingfthe ,reactibh substituted-areas asfrnethizll Whilethe dye anir'prmtine hastecorii'positions" '75" whole tnortugh-lydiiixea to produce "a printing ."stirfiedluntil the carbonates dissolved. Heating wasdisco btit stirring was continued until= the-tempt tu'r'e reached approximately 150 at which time 700 parts of sodium sulfoxylate formaldehyde were dissolved therein, 600 parts of glycerine were added and the paste bulked to about" 1 03000 parts. Stirring was continued until the paste cooled to room temperature. In the succeeding ex'amples this paste isreferred td'as Thickener A. l I

. Example 2 720 parts of 3-2 British gum and '720 parts of KAC-4 um (Stein Hall)" were added to 5600 parts of water and" heated over a s'teajr'nv bathfor approximately 1 /2 hours after the temperature reached about 1185 1909" Fi The sourceof heat wasthen removed but stirring wascontinued untilfthetemperature"decreased to F. at which time 1 200"parts of potassium carbonate which had been previously" dissolved'in 1000 parts of water was added to 'th{e cooked gtm; 1560 parts of sodium sulfoxylate formaldehyde were" dissolved in 1500 parts of water-at a temperat re of abo-ut"'1'4' 0 1 FL andfaddedtoj the common mixturewith stirringuntil the whole was tnqr'cug fy:

the ucceeq'in examples hickenenBJ i amplestwotyliesbf aging;

se ar referred toas rg'ii- I a The r u ar-aging. accomplished simply by treatin -"the steam ager. In-thewrappedfagein" he-printwas around a ro'd 'o approximately"%-ini:h

I color without passingthroulgh thj' wrapped-roll was 'aged'fbr ab out 1o urea and parts of normalj'butafiol odor ftmmtnia"practicauyuisapp fed; To

cose rayon fiat crepe. The printed pie'ces w e dried in a hot air oven, aged, both open and wrapped, at about 104. 0., oxidized, soaped at the boil for five minutes with a0.1% soap solutionrr nse a d ir ned y T e. p ts. rcm i pa o in n the butylzc b ma e ticeably stronger and brighterthan those ob;

Example J j H :-Additional':porti ons oi the 1 two printing :pastes of; Exampley3 were preparedand a third portion was 1-1 prepared, in which five .parts of diethylene glycol ",was used to, replace the five parts of butyl carbamate. These samples were allowed to stand at room temperature in covered vessels and the printing procedures of Example 3 were repeated at periodic-intervals for several weeks. Comparisorifofthe prints showedlthatthe color yields obtained from the pastes containing the carbamate, when tested periodically, decreased only slowly whereas those from the other samples decreased rapidly. The decrease was most noticeable in the case of the glycol-containing paste.

Example 6' .5 parts of a dispersible Golden Orange G powder (Color Index 1096), prepared according to U. S. Reissue Patent 21,402 and containing about 1 part of real dye, were made into a paste with 5 parts of water and 90 parts of Thickener B. A second 5 parts of Golden Orange R powder Was pasted with 5 parts of a 6% dispersion of butyl Example 7 The procedure of Example 6 was duplicated except that 5 parts of a dispersible Dark Blue BO powder (Color Index 1099), prepared according to U. S. Reissue Patent 21,402 and containing approximately 2 parts of real dye were used in place of the Golden Orange G. Prints from the paste containing the carbamate were distinctly stronger than from the pastes containing only color.

Example 8 The procedure of Example 6 was repeated, replacing the Golden Orange G with 5 parts of a dispersible Hydron Orange R powder (Color Index 1217) and containing 1.2 parts of real dye.

.containapproximatelyjmyt we en in edpn t A a n: h p nts. v bl i ll fiii iltqmfit i a te 1 0- taining the butyl carbamatewere much stronger both on pigmented rayon and cotton pieces than those obtained from.thepaste in which no printing assistant was used.

A sample of Hydro f-Orangej'R wet *pre cake was= dispersedtheedium aa of disulfo dinaphth lrnethane all ofthis slurry waspasted' with ammo pans of Thi ckenerh of the printing colori was wa. t erandflfijfparts offfa 6" a dispersion ofbutyl carbamatahdpa'rts-oi Thickener B9 FA third 10 parts of color was mixedwith loparts of a 6% solution of butyl carbamate in alcohol and 80 parts of Thickener. B. Each of these pastes 1 mol portion of urea and 2 mol portions of octyl alcohol were refluxed until the ammoniacal odor given off by the reaction had disapeared.

Example 11 in which R isa member selected from the group consisting of the primary and secondary alkyl radicals of from 3-12 carbon atoms, and R1 and R2 are members selected from the group consisting of hydrogen and the alkyl radicals of from 1-4 carbon atoms, R1 and R2 being identical when both are alkyl radicals.

2. A color composition comprising a vat dye and a crystallizable alkyl carbamate of the formu 9.

in which R is a member selected from the group 7 consisting of the primary and secondary alkyl radicals of from 4-8 carbon atoms.

3. A color composition according to claim .2 in which R is the n-butyl radical.

4. A color composition according to claim 2 in which R is an ethyl butyl radical.

5. A color composition according to claim .2 in which R is an octyl radical.

6. A dye powder composition comprising a vat & A dye powder composition aecord-ing to claim 6 which Bis an ethyl-buty l radicab 19 A iiye powder compositicn acccrfiin g-tociaim Gin/Which R-is an octyl-radical, v

1- P mes-P q i iq qq i 't a vat dye, a. thickener and a crysta llizablealkyl carbarnate oftheibrrnuia.

ifi Hits-"a members'ieta from the group in which is a member selectediromjthesgroup ne t epf t e ne me and i ew d alkyl radicals of from -8 carbon; atoms-said vpt\.ste-1c e- 8.. lb fe i emg u nei j z? d of high autodispersibility and the printing: assistant with the t hickener.

m which R is a member selected from the groc consisting of the 'primary and secondary allay radicals'df fr'o'm4-8 carbon atoms:

ROY -H-ERMAN CHESTER ALBERT AMICK.

REFERENCES CITED The fdliowing references are of record in the file ofthis patent: I I

UNITED STATES'PATENTS- Number Name U Dat'e' zgmsy so' Meyer Jan. 10, 1939 2,047,069 l-Ietit'rih Jl'ilyf7, 19 36 2,116,521 Kritchii sky May 10, 1,964,564 Ulrich June 26, 1934 1,933,945 Ulrich Nov. 7, 1933 $184,495 Graenecher Dec- 26,1939 21-17523 Paquin 'et a1. May 117, -193'a 1356,43; Schmidt ..'May 3, 1932 2,090,511 Cross1ey Aug lfl, 193? FOREIGN PATENTS v 7 Number Country. Date, 156,726 Switzerland -a Feb. 16,-1933 514,738 Germany -d a Dec. 17, 1930 

